KR20180102051A - Aqueous polyurethane resin composition, and optical film using the composition - Google Patents

Abstract

Provided is a polyurethane resin composition which is excellent in moisture resistance, transparency, adhesiveness to a photo-curable resin, blocking resistance, less warpage, and is suitable for optical film applications.
(A) prepared by reacting a polyol (a), a polyisocyanate (b) and an anionic group-introducing agent (c) and a specific (meth) acrylic compound (B) And the ratio of the prepolymer (A) to the (meth) acrylic compound (B) is from 100: 1 to 30 (by mass ratio), and then the urethane prepolymer composition Based polyurethane resin composition obtained by dispersing in water such that the concentration of the prepolymer composition is 10 to 70 mass% and reacting the urethane prepolymer (A) in the obtained aqueous dispersion with the chain extender (C).

Description

Aqueous polyurethane resin composition, and optical film using the composition

The present invention relates to an aqueous polyurethane resin composition useful as a material for an adhesive layer between a polyester resin layer and a photocurable resin layer. The present invention also relates to an optical film using the water-based polyurethane resin composition, for example, a prism sheet.

BACKGROUND ART [0002] Various optical films are used in liquid crystal displays used in televisions, personal computers, and the like, and prism sheets are used as parts constituting a backlight unit of a liquid crystal display in order to improve brightness. In the prism sheet, brightness is improved by the function of condensing the outgoing light emitted from the light guide in the direction of the liquid crystal panel by the prism inclined surface. The prism sheet is composed of a polyester resin such as PET and a photocurable resin on which a prism pattern is formed. A variety of adhesive layers have been used to bond the polyester resin and the photocurable resin. As a process for producing a prism sheet, a polyester resin is heated and melted, a polyester resin extruded by a single screw or twin screw extruder is made into a film by a stretching machine, the adhesive layer is coated on the surface of the polyester resin, And a method of bringing the photocurable resin into close contact with each other.

Japanese Laid-Open Patent Publication No. 2011-140139 Japanese Laid-Open Patent Publication No. 2012-194308

The prism sheet is required to have high light transmittance to ultraviolet rays and visible light in a relatively low wavelength region, and heat resistance to maintain performance at high temperatures such as in summer. As a result, the adhesive layer for bonding the polyester resin and the photocurable resin needs to have equivalent performance. The adhesive layer is also required to have low adhesiveness to the photocurable resin or adhesion (blocking property) between the films when the films are superimposed on each other. As an adhesive layer of such a prism sheet, for example, Patent Documents 1 and 2 disclose an adhesive layer using an aqueous polyurethane resin composition. By these adhesive layers for prism sheets, it is possible to provide a prism sheet having flexibility due to urethane, high light transmittance and heat resistance. However, the adhesiveness between the adhesive layer and the photocurable resin and the improvement in the blocking property between the adhesive layers are not at a satisfactory level. The prism sheet which is a component of the backlight unit of the liquid crystal display still needs to be improved in adhesion between the polyester resin layer and the photocurable resin layer constituting the prism sheet.

Therefore, the present inventors have made an earnest effort to improve the adhesion of the adhesive layer to the photopolymer resin and the blocking resistance when an aqueous polyurethane resin composition is used as the adhesive layer of the prism sheet.

As a result, the present inventors have found that by using a (meth) acrylic compound as a raw material in combination, an aqueous polyurethane resin composition having good adhesion to a photocurable resin and improved blocking resistance can be obtained. That is, the present invention is as follows.

(1) a urethane prepolymer (A) obtained by reacting a polyol (a), a polyisocyanate (b) and an anionic group-introducing agent (c) (Meth) acrylic compound (B) represented by the formula (2) in such a ratio that the ratio of the yrete prepolymer (A) and the (meth) acrylic compound (B) is 100: 1-30 And then the urethane prepolymer composition is dispersed in water such that the concentration of the urethane prepolymer composition is 10 to 70% by mass, and the urethane prepolymer (A) in the obtained aqueous dispersion is subjected to a color change (C). ≪ / RTI >

(Wherein R ¹ to R ² represent a hydrogen atom or a methyl group, R ³ and R ⁴ each independently represent a divalent hydrocarbon group having 2 to 4 carbon atoms, R ⁵ represents a sulfur atom or a hydrocarbon group, m and n Each represent an integer of 0 to 10).

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group)

(Invention 2), the (meth) acrylate compound (B) has the general formula is a compound represented by (1), wherein R ⁵ represents the formula of (1), a single bond, a methylene group, -CH (CH ₃₎ -, -C (CH ₃ ) ₂ -, and any one of the functional groups represented by the following general formulas (3-1) to (3-7).

(m represents an integer of 4 to 12)

(Inventive 3) The polyol (a) is at least one selected from the group consisting of a polyester polyol (a1), a polycarbonate diol (a2), a polyether polyol (a3) By weight based on the weight of the water-based polyurethane resin composition.

(Inventive 4) The aqueous polyurethane resin composition according to any one of Inventions 1 to 3, wherein the polyol (a) is at least one or more selected from a polycarbonate diol (a2).

(Invention 5) The polyol (a) is characterized in that the polyol (a) is composed of a high molecular weight polyol (a-HM) having a number average molecular weight of 1,500 to 5,000 and a low molecular weight polyol , And the aqueous polyurethane resin composition according to any one of Inventions 1 to 4.

(Inventive 6) The aqueous polyurethane resin composition according to any one of Inventions 1 to 5, wherein the acid value of the yretin prepolymer (A) is in the range of 30 to 80 mgKOH / g.

(7) An optical film comprising an aqueous polyurethane resin composition according to any one of (1) to (6).

(Invention 8) A prism sheet comprising a layer comprising an aqueous polyurethane resin composition according to any one of inventions 1 to 6, a base film, and a layer of a cured product of a photocurable resin.

According to the present invention, there is provided a waterborne polyurethane resin composition which has good adhesiveness between a polyester resin and a photo-curable resin and is hard to cause blocking between films. Further, the present invention provides a prism sheet which is suitable for a component of a backlight unit of a liquid crystal display, has less warpage due to curing shrinkage, and is excellent in moisture resistance and transparency.

Hereinafter, embodiments of the waterborne polyurethane resin composition of the present invention will be described. The waterborne polyurethane resin composition of the present invention is prepared by first mixing a urethane prepolymer (A) obtained by reacting a polyol (a), a polyisocyanate (b), and an anionic group-introducing agent (c) (A) is dispersed in water so as to have a concentration of 10 to 70 mass%, and then the urethane prepolymer (A) in the obtained dispersion is crosslinked (crosslinked) to the chain elongation agent (C) . The (meth) acrylic compound in the present specification is a general term for a compound selected from any one of an acrylic compound having at least one acrylic group in the molecule and a methacrylic compound having at least one methacryl group in the molecule. The (meth) acrylic group represents an acryl group or a methacryl group.

[Yuretene prepolymer (A)]

The urethane prepolymer (A) is a component of a urethane prepolymer composition which is a raw material of the aqueous polyurethane resin composition of the present invention. The urethane prepolymer (A) is obtained by reacting the polyol (a), the polyisocyanate (b), and the anionic group-introducing agent (c). Hereinafter, the constituent components of the urethane prepolymer (A) of the present invention will be described.

(Polyol (a))

As the polyol (a), for example, polyester polyol (a1), polycarbonate diol (a2), polyether polyol (a3) and polyol (a4) having a number average molecular weight of less than 200 may be used.

As the polyester polyol (a1), for example, a compound obtained by esterification reaction of a low molecular weight polyol and a polycarboxylic acid, a compound obtained by ring-opening polymerization reaction of a cyclic ester compound such as? -Caprolactone,? -Valerolactone, And copolyesters thereof, and the like.

Examples of the low molecular weight polyol include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, , Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1 , 5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, Diene, 1,9-nonene diol, 1,10-decene diol, 1,11-undecene diol, 1,12-dodecane diol, 2-methyl- Ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol , 2-methyl-1,8-octanediol, and other aliphatic diols such as glycerin, trimethylol propane, ditrimethylol propane, tristrimethylol propane, Aliphatic polyols such as pentaerythritol are used. Examples of the low molecular weight polyol include aliphatic cyclic structure-containing polyols such as 1,4-cyclohexane dimethanol and hydrogenated bisphenol A, bisphenol A, alkylene oxide adducts of bisphenol A, bisphenol S, bisphenol A Bisphenol-type polyol such as an alkylene oxide adduct of S may also be used. As these low molecular weight polyols, an aliphatic polyol or an aliphatic cyclic structure-containing polyol is preferable, and an aliphatic diol is particularly preferable.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, succinic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, dimeric acid, 1,4-cyclohexane dicarboxylic acid, Terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimellitic acid, isophthalic acid, terephthalic acid, Aromatic polycarboxylic acids such as pyromellitic acid, and anhydrides or ester derivatives thereof. The compound used as the polycarboxylic acid may be a single compound or a mixture of two or more compounds. As such polycarboxylic acids, aliphatic polycarboxylic acids are preferred, and aliphatic dicarboxylic acids are particularly preferred.

As the polyester polyol (a1), a polyester polyol having no aromatic cyclic structure is preferable, and a polyester polyol obtained by reacting an aliphatic polyol and an aliphatic polycarboxylic acid is more preferable. In order to improve the heat resistance and light transmittance of the prism sheet using the waterborne polyurethane resin composition of the present invention, an aliphatic polyol having 2 to 6 carbon atoms and an aliphatic polycarboxylic acid having 2 to 6 carbon atoms are reacted The obtained polyester polyol is particularly preferable as the polyester polyol (a1).

As the polycarbonate diol (a2), those obtained by reacting a carbonate ester and / or a phosgene with a polyol described later can be used. As the carbonic ester, for example, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, diphenyl carbonate, dinaphthyl carbonate, phenylnaphthyl carbonate and the like can be used.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5- 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonene diol, 1,10-decene diol, 1,11-undecene diol, 1,12-dodecane diol, 2-methyl- Ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2- Methyl-1,8-octanediol, and the like. As the polyol, low molecular weight dihydroxy compounds such as 1,4-cyclohexane dimethanol, hydroquinone, resorcin, bisphenol A, bisphenol F, and 4,4'-biphenol; Polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; Polyester polyol such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone may also be used. As the polyol used for the production of the polycarbonate diol (a2), an aliphatic diol is preferable, and 1,6-hexanediol is more preferable.

As the polyether polyol (a3), one or two or more compounds having two or more active hydrogen atoms may be used as an initiator and addition-polymerized with an alkylene oxide.

Examples of the initiator include water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, Diethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol 1,10-decene diol, 1,11-undecene diol, 1,12-dodecane diol, 2-methyl-1,3-propane diol , Neopentylglycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, Methyl-1,8-octanediol, glycerin, diglycerin, trimethylol propane, ditrimethylol propane, tristrimethylol propane, 1,2,6- Diethanolamine, triethanolamine, triisopropanolamine, pentaerythritol, dipentaerythritol, sorbitol, sucrose, ethylenediamine, N-ethyldiethylenetriamine, 1,2-diaminopropane, 1,3 -Diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, diethylene triamine, phosphoric acid, acidic phosphate esters and the like can be used.

As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like can be used.

Examples of the polyol (a4) having a number average molecular weight of less than 200 include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl- Diethylene glycol, triethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentylglycol, 3-methyl- 2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Diol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8- Aliphatic diols such as octane diol, 2-methyl-1,8-octane diol and 1,9-nonene diol; Alicyclic diols such as cyclohexane dimethanol and cyclohexane diol; Trihydric or higher polyols such as trimethylolethane, trimethylolpropane, hexitol, pentitol, glycerin, pentaerythritol and the like can be used.

The polyol (a) may be any of the polyester polyol (a1), the polycarbonate diol (a2), the polyether polyol (a3) and the low molecular polyol (a4) having a number average molecular weight of less than 200, The use of the polycarbonate diol (a2) is preferable in terms of heat resistance and light transmittance of the prism sheet formed using the aqueous polyurethane resin composition of the invention. As such a polycarbonate diol (a2), a polycarbonate diol having no aromatic cyclic structure is more preferable, and a polycarbonate diol having a skeleton of 1,6-hexanediol is particularly preferable.

In the present invention, as the polyol (a), two kinds of polyols having different number average molecular weights may be used in combination. The polyol (a) has a number average molecular weight of 300 to 1000, preferably a high molecular weight polyol (a-HM) having a number average molecular weight of 1500 to 5000, preferably 1700 to 3000, more preferably 1800 to 2200 Molecular weight polyol (a-LM) having a molecular weight of 400 to 700. The ratio of the high molecular weight polyol (a-HM) to the low molecular weight polyol (a-LM) is not limited, but the proportion of the high molecular weight polyol (a-HM) in the total amount of the polyol (a) By mass, more preferably 3 to 50% by mass, and particularly preferably 5 to 30% by mass.

By using the high molecular weight polyol (a-HM) and the low molecular weight polyol (a-LM) as the polyol (a) of the present invention in combination, it is possible to reduce the blocking of the film made of the aqueous polyurethane resin composition of the present invention. Although the structure of the blocking reduction is not sufficiently clarified yet, the use of the low molecular weight polyol (a-LM) reduces the amount of the soft segment in the resin, and accordingly, the microbrown motion of the soft segment inside the aqueous polyurethane resin composition Is reduced, and as a result, it is presumed that mutual adhesion of the aqueous polyurethane resin composition is inhibited. In addition, when the polyol (a) contains a high molecular weight polyol (a-HM), the viscosity of the resulting urethane prepolymer (A) is lowered, and an advantage is obtained in that the urethane prepolymer (A) is easy to handle.

(Polyisocyanate (b))

As the polyisocyanate (b), for example, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate Aromatic diisocyanates such as cyanate; Hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethyl Diisocyanate containing an aliphatic or alicyclic structure such as xylylene diisocyanate can be used. The aromatic diisocyanate or a compound obtained by dimerizing the aliphatic or alicyclic structure-containing diisocyanate can also be used. These compounds may be used alone, or two or more of these compounds may be used in combination.

In order to further improve light transmittance and heat resistance in a low wavelength region such as an ultraviolet ray or a visible light ray of a prism sheet formed using the water-based polyurethane resin composition of the present invention, an aliphatic cyclic structure (b) as the polyisocyanate Containing diisocyanate is preferable, and 4,4'-dicyclohexylmethane diisocyanate or isophoronediisocyanate is more preferable. 4,4'-dicyclohexylmethane diisocyanate is particularly preferable for the heat resistance of the prism sheet.

(Anionic group-introducing agent (c))

Examples of the anionic group-introducing agent (c) include polyols containing carboxyl groups such as dimethylol propionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid and the like, Sulfonic acid group-containing polyols such as oleic acid and oleic acid-sulfonic acid groups. In view of easy availability, polyols containing a carboxyl group are preferable, and dimethylol propionic acid is more preferable.

(amounts of (a), (b), and (c)

Generally, when a urethane prepolymer is prepared by reacting a polyol, a polyisocyanate, and an anion-introducing agent, the total isocyanate group equivalent (NCO) of the polyisocyanate, the polyol and the anionic group introduction The terminal structure of the urethane prepolymer obtained differs depending on the ratio of the total hydroxyl equivalent (OH) contained in the prepolymer. When the NCO / OH is less than 1.0, that is, when the hydroxyl group in the reaction component is excessive, a urethane prepolymer having a terminal hydroxyl group is obtained. When the ratio NCO / OH is 1.0 or more, that is, when the isocyanate group in the reaction component is excessive, a urethane prepolymer having an isocyanate group at the terminal group is obtained. The urethane prepolymer having an isocyanate group at the terminal is higher in water-dispersibility than the urethane prepolymer having a hydroxyl group at the terminal, and is easily polymerized by a chain extender. Therefore, as the urethane prepolymer (A) of the present invention, a urethane prepolymer whose terminal group is an isocyanate group is preferable.

However, when the ratio NCO / OH is 1.0 or more and less than 1.1, a relatively high molecular weight urethane prepolymer is obtained, and such a high molecular weight urethane prepolymer tends to be poor in water dispersibility. In this case, there is a possibility that the storage stability of the ultimately obtained aqueous polyurethane resin composition is deteriorated. When the ratio NCO / OH exceeds 2.5, the product contains a high concentration of isocyanate groups. Therefore, when the obtained prepolymer is dispersed in water, the isocyanate group reacts with water to generate carbon dioxide, There is a possibility of causing problems in manufacturing. In this case, there is also a possibility that the adhesion between the coating film made of the obtained waterborne polyurethane resin composition and the substrate is lowered.

Therefore, when preparing the urethane prepolymer (A) of the present invention, the polyol (a), the polyisocyanate (b) and the anion initiator (c) are mixed with the polyisocyanate (b) (NCO / OH) of the total isocyanate group equivalent (NCO) of the polyol (a) and the total hydroxyl equivalent (OH) contained in the polyol (a) and the anionic group-introducing agent (c) is preferably 1.1 to 2.5 (A), (b), and (c) are blended so that the amount of the component (A) is 1.2 to 2.0, particularly preferably 1.3 to 1.8.

(The acid value of the urethane prepolymer (A)

In order to reduce the blocking of the aqueous polyurethane resin composition of the present invention, the acid value of the above-mentioned urethane prepolymer (A) is preferably 35 to 90 mgKOH / g, more preferably 40 to 80 mgKOH / g , Particularly preferably 50 to 70 mg KOH / g. The anionic group-introducing agent (c) is used in an amount corresponding to the acid value of the urethane prepolymer (A). The acid value of the above-mentioned urethane prepolymer (A) is a theoretical value obtained from the amount of the reaction components of the urethane prepolymer (A). When an inert solvent is used to prepare the urethane prepolymer (A) as described later, the measured value of the acid value of the obtained urethane prepolymer (A) varies from the above-mentioned theoretical value. The following relationship exists between the above-mentioned theoretical value and the measured value.

Acid value (theoretical value)

(A) + (b) + (c): sum of mass} (mass) (mass)

(catalyst)

In the production of the urethane prepolymer (A) of the present invention, a catalyst may be used if necessary. As such catalysts, there may be mentioned, for example, N, N, N ', N'-tetramethylethylenediamine, N, N, N' , N '' -pentamethyldiethylenetriamine, N, N ', N' ', N' '- pentamethyl- (3-aminopropyl) , N " -pentamethyldipropylenetriamine, N, N, N ', N'-tetramethylguanidine, 1,3,5-tris (N, N- dimethylaminopropyl) hexahydro-S- , N, N ', N'-tetramethylhexamethylenediamine, N-methyl-N' - (2- Dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis Tertiary amines such as dimethyl lauryl amine, 1-methyl imidazole, 1,2-dimethyl imidazole, 1-isobutyl-2-methyl imidazole and 1- Ah Min is available. In addition, quaternary ammonium salts such as tetraalkylammonium halides such as tetramethylammonium chloride and the like, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraalkylammonium 2-ethylhexanoate, Dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dichloride, dioctyl tin diacetate, dibutyl tin diacetate, stearic acid diester, Organometallic catalysts such as laurate, lead octanoate, lead naphthenate, nickel naphthenate and cobalt naphthenate can also be used. These catalysts may be used alone, or two or more of them may be used in combination. Of these catalysts, organometallic catalysts are preferable, and dibutyltin dilaurate or dioctyltin dilaurate is more preferable in view of low sulfur denaturation and good reactivity. The amount of such catalyst to be used is not particularly limited, but it is preferably 0.001 to 1% by mass based on the total amount of the polyol (a), the polyisocyanate (b), and the anionic group-introducing agent (c) Is 0.01 to 0.1% by mass.

(Crosslinking agent)

In the production of the urethane prepolymer (A) of the present invention, a crosslinking structure can be introduced into the urethane prepolymer (A) using a crosslinking agent. As the crosslinking agent, a crosslinking agent usually used in the synthesis of the urethane prepolymer may be used without limitation. Examples of the crosslinking agent include melamine, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylated methylol melamine, butylated methylol melamine , Melamine resin and the like can be used. The cross-linking agent used in the present invention is preferably a low-cost melamine because of its excellent dispersibility to polyurethane. The amount of the crosslinking agent to be used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass based on 100 parts by mass of the polyol (a).

(Preparation of urethane prepolymer (A)

The urethane prepolymer (A) used in the present invention can be produced by reacting the polyol (a), the polyisocyanate (b), the anion initiator (c) and optional catalyst and / or crosslinking agent in an inert solvent In the presence of a catalyst. As the inert solvent used there may be used acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, N-ethyl-2- have. When a solvent having a boiling point of 100 DEG C or lower is used, it is preferable to synthesize the aqueous polyurethane resin of the present invention and then remove the solvent by distillation under reduced pressure. The amount of the solvent to be used is not particularly limited, but is preferably 3 to 200 parts by mass based on 100 parts by mass of the total amount of the raw materials of the urethane prepolymer (A). The obtained urethane prepolymer (A) is dispersed in water together with a (meth) acrylic compound (B) described later to form a urethane prepolymer composition.

[(Meth) acrylic compound (B)]

The (meth) acrylic compound (B) is a component of a urethane prepolymer composition which is a raw material of the aqueous polyurethane resin composition of the present invention. The (meth) acrylic compound (B) is dispersed in water together with the above-mentioned urethane prepolymer (A) to form a urethane prepolymer composition. The (meth) acrylic compound (B) of the present invention is an acrylic compound represented by the following general formula (1) or general formula (2).

(Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, R ³ and R ⁴ each independently represent a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ⁵ represents a sulfur atom or a hydrocarbon group. m and n each represent an integer of 0 to 10.)

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group)

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ³ and R ⁴ are each independently a divalent hydrocarbon group having 2 to 4 carbon atoms, for example, 1,2-ethanediyl group, 1,1-ethanediyl group, 1,3-propanediyl group, A 2-propane diyl group, a 1,1-propane diyl group, a 2,2-propane diyl group, and a 1,4-propane diyl group. In view of the availability of the (meth) acrylic compound (B), preferred R ³ and / or R ⁴ are 1,2-ethane diyl group and / or 1,2-propane diyl group.

In the above formula (1), R ⁵ represents a sulfur atom or a hydrocarbon group. R ^{5 which} is a hydrocarbon group is, for example, a methine dylyl group, a 1,2-ethane dylyl group, a 1,1-ethane dylyl group, a 1,3-propane dylyl group, , 1-propane diyl group, 2,2-propane diyl group, 1,4-propane diyl group, 1,5-pentane diyl group, Methyl-1,3-propane dylyl group, 2-methyl-1,2-propane dylyl group, 1-methyl-1,4-butenediyl group, 2- 1,4-butenediyl, and 1,4-butenediyl, and also include, for example, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cycloheptanediyl, An aromatic dyiyl group such as an alicyclic dyellow group, a benzene dylyl group, a toluene dylyl group, a naphthalenediyl group, an anthracene dylyl group, a phenanthrene dylyl group, and a fluorenediyl group. (Meth) acrylate from the viewpoint of easy availability of the compound (B), preferable R ⁵ is a single bond, a methylene _{group, -CH (CH 3) -,} -C (CH 3) 2 -, the following formula (3-1 ) To (3-7).

(m represents an integer of 4 to 12)

In the above formula (1), m and n each represent an integer of 0 to 10. From the viewpoint of the compatibility between the urethane prepolymer (A) and the (meth) acrylic compound (B) in the aqueous dispersion and the water resistance of the coating film when the aqueous polyurethane resin composition is used as a coating film, , and n is preferably 0 to 5, more preferably 0 to 3. When m or n is larger than 10, the compatibility of the urethane prepolymer (A) and the (meth) acrylic compound (B) in the aqueous dispersion is good, but the water resistance of the coating film formed of the aqueous polyurethane resin composition is remarkably deteriorated. In addition, the number of m and n is an average value using a constant value.

A preferred compound as the (meth) acrylic compound (B) represented by the formula (1) is represented by any one of the following formulas (4-1), (4-2), and (4-3).

(p and q are each independently an integer of 1 to 3)

[Yleetene prepolymer composition]

(Water dispersion)

In the present invention, a urethane prepolymer composition containing a urethane prepolymer (A) and a (meth) acrylic compound (B) is dispersed in water. The method of dispersing the urethane prepolymer composition in water is not particularly limited, and for example, the following prepolymer mixing method and phase transfer method can be used.

(Prepolymer Mixing Method) The urethane prepolymer (A) and the (meth) acrylic compound (B) are mixed. An anionic group neutralizing agent may be added together with the (meth) acrylic compound (B). The resulting mixture is poured into water to disperse the urethane prepolymer mixture in water. In addition, an emulsifier may be added to water before the mixture is added. Thus, water dispersion of the urethane prepolymer composition of the present invention is completed.

(Phase Transfer Method) The urethane prepolymer (A) and the (meth) acrylic compound (B) are mixed. Water is added to the resulting mixture to obtain a yutein prepolymer mixture and a dispersion of water. Further, water added with an anionic group neutralizing agent and / or an emulsifying agent may be introduced in advance. Thus, water dispersion of the urethane prepolymer composition of the present invention is completed.

(Anionic group neutralizing agent)

Examples of the anionic group neutralizing agent include trialkyl amines such as trimethylamine, triethylamine and tributylamine; N, N-dialkylalcohols such as N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine and 1-dimethylamino- Tertiary amine compounds of trialkanolamines such as amines, N-alkyl-N, N-dialkanolamines and triethanolamines; Basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. These compounds may be used alone, or two or more of these compounds may be used in combination. From the viewpoint of improving the weather resistance and water resistance of the dried product of the aqueous polyurethane resin composition of the present invention, it is preferable to use an anionic group neutralizing agent having high volatility which is easily dissociated by heat. Particularly preferred anionic group neutralizing agents are trimethylamine and / or triethylamine.

The amount of the anionic group neutralizing agent to be used is not particularly limited as far as the storage stability of the aqueous polyurethane resin composition, the mechanical properties such as the strength of the coating film formed of the aqueous polyurethane resin composition, the water resistance of the coating film formed of the aqueous polyurethane resin composition, , Preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents based on 1 equivalent of an anionic group.

(Emulsifier)

A known surfactant may be used as the emulsifier. For example, cationic surfactants such as general anionic surfactants and nonionic surfactants, surfactants such as primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, and pyridinium salts, Amphoteric surfactants such as active agents, betaine type, sulfuric acid ester type and sulfonic acid type can be used.

Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate and ammonium dodecyl sulfate, sodium polyoxyethylene alkyl ether sulfates such as sodium dodecyl polyglycol ethersulfate and ammonium polyoxyethylene alkyl ether sulfates Ethylene ether sulfates; Alkali metal salts of sulfonated paraffins, and ammonium salts of sulfonated paraffins; Fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abietate; Sodium benzene sulfonate, and alkali metal sulfates of alkali phenol hydroxyethylene. In addition, it is also possible to use polyalkylene sulfates such as high alkyl naphthalenesulfonates, naphthalenesulfonic acid phomalin condensates, dialkylsulfosuccinates, polyoxyethylene alkylsulfate salts, polyoxyethylene alkylarylsulfate salts, polyoxyethylene ether phosphates, polyoxyethylene alkyl Acetic acid salt, N-acyl amino acid salt, and N-acyl methyl taurine salt.

As the nonionic surfactant, fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate, polyoxyethylene glycol fatty acid esters and polyglycerin fatty acid esters can be used. Also, ethylene oxide and / or propylene oxide adducts of alcohols having 1 to 18 carbon atoms, ethylene oxide and / or propylene oxide adducts of alkylphenol, ethylene oxide and / or propylene oxide adducts of alkylene glycol and / Water can also be used.

The alcohols having 1 to 18 carbon atoms constituting the nonionic surfactant are, for example, alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol 3 amyl alcohol, hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, and stearyl alcohol.

The alkylphenols include, for example, phenol, methylphenol, 2,4-dodecylbutylphenol, 2,5-dodecylbutylphenol, 3,5-dodecylbutylphenol, 4- 4-octylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- - dimethylheptyl) phenol, naphthol, bisphenol A, and bisphenol F, and the like.

The alkylene glycol may be, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, Ethyl-1,3-propanediol, 1,4-butanediol, neopentylglycol, 1,5-pentanediol, 3-methyl- 2,4-diethyl-1,5-pentanediol, and 1,6-hexanediol.

The alkylenediamine is, for example, a compound in which the alcoholic hydroxyl group of the alkylene glycol described above is substituted with an amino group. As the ethylene oxide and propylene oxide adducts, both random adducts and block adducts can be used.

Examples of the cationic surfactant include lauryl trimethylammonium chloride, stearyl trimethylammonium chloride, distearyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, lauryl benzyl dimethyl ammonium chloride, Methyl ammonium chloride, alkyl pyridinium bromide, and imidazolinium laurate.

Examples of the amphoteric surfactant include coconut fatty acid amide propyl dimethylacetate betaine, lauryl dimethyl amino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, lauryl Beta-type amphoteric surfactants such as hydroxypropovataine, lauroyl amide ethylhydroxyethyl carboxymethyl betaine and metal salts of hydroxypropyl phosphoric acid, amino acid type amphoteric surfactants such as metal salts of beta laurylaminopropionic acid, An ester type amphoteric surfactant and a sulfonic acid type amphoteric surfactant can be used.

In view of easy availability and low cost, nonionic surfactants are preferred as emulsifiers, fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate, ethylene oxides of alcohols having 1 to 18 carbon atoms, / Propylene oxide adduct are more preferable.

The amount of the emulsifier to be used is not particularly limited, but is preferably 0 to 30 parts by mass based on 100 parts by mass of the total amount of the urethane prepolymer composition, from the viewpoints of water resistance and the like of the coating film comprising the aqueous polyurethane resin composition, And preferably 0 to 20 parts by mass. When the water resistance of a coating film composed of a water-based polyurethane resin composition is particularly emphasized, it is preferable to minimize the amount of the emulsifier used.

(The amounts of the urethane prepolymer (A) and the (meth) acrylic compound (B)

The amount of the (meth) acrylic compound (B) in the urethane prepolymer composition is preferably from 1 to 30 parts by mass, more preferably from 3 to 25 parts by mass, and particularly preferably from 1 to 30 parts by mass based on 100 parts by mass of the urethane prepolymer (A) By weight is 5 to 20% by weight. When the amount of the (meth) acrylic compound (B) to be blended is less than 1 part by mass based on 100 parts by mass of the urethane prepolymer (A), adhesion with the photocurable resin is remarkably reduced. When the blending amount is more than 30 parts by mass, the storage stability of the prepared water-based urethane resin composition is remarkably lowered.

[Waterborne Polyurethane Resin Composition]

(Make-up preparation agent (C))

The aqueous polyurethane resin composition of the present invention is characterized in that the urethane prepolymer (A) contained in the urethane prepolymer composition is dissolved in water .

Examples of the chain extender (C) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, Triethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentylglycol, 3-methyl- Diol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl- Diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2 -Methyl-1,8-octanediol, 1,9-nonene diol, and the like can be used. Further, alicyclic diols such as cyclohexane dimethanol and cyclohexane diol, low-molecular dies such as ethylene diamine, propylene diamine, hexamethylene diamine, tolylene diamine, piperazine, 2- Amines, polyoxypropylene diamine, polyoxyethylene diamine, and other polyetherdiamines.

As the make-up dispersant (C), there can be used at least one member selected from the group consisting of menthenediamine, isophorone diamine, norbornenediamine, aminoethylaminoethanol, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (Aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspireo (5,5) undecane; (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diamino dimethyldiphenylmethane, di Polyamines of aromatic di-amines such as aminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, and?,? '- bis (4-aminophenyl) Can be used. (N, N-dimethylsemecarbazide), 1, < RTI ID = 0.0 > Hydrazines such as 1,1 ', 1'-tetramethyl-4,4' - (methylene-di-para-phenylene) diaminocarbazide, hydrazine hydrazine and water can also be used.

From the viewpoints of availability and ease of reaction, preferred is a diamine, hydrazide, hydrazine hydrazine and water as the chain extender (C), and preferred are ethylene diamine, adipic acid dihydrazide, hydrazine, water Is particularly preferable.

The amount of the above-mentioned chain extender (C) to be used is preferably set such that the amount of the above-mentioned chain extender (C) to be used is not more than the amount of the isocyanate group equivalent contained in the urethane prepolymer It is preferable to set the amount such that the ratio of the equivalent amount of the isocyanate contained in the chain extender (C) is in the range of 0.1 to 1.0.

(Polyurethane resin)

The aqueous polyurethane resin composition of the present invention contains a specific polyurethane resin as a main component. The polyurethane resin contained in the aqueous polyurethane resin composition of the present invention is a polyurethane resin obtained by reacting a polyurethane (a), a polyisocyanate (b), and an anionic group-introducing agent (c) (A) is formed in the presence of (meth) acrylic compound (B) in water. The repeating unit of the polyurethane resin contained in the waterborne polyurethane resin composition of the present invention is not constant, and the structure and the number of repeating units vary widely. Therefore, the structure of the polyurethane resin contained in the waterborne polyurethane resin composition of the present invention is very complicated. Therefore, the structure of the polyurethane resin ultimately contained in the waterborne polyurethane resin composition of the present invention can not be uniformly represented by any kind of general formula. Therefore, in the present invention, it is preferable that the "aqueous polyurethane resin composition" containing the polyurethane resin as described above is used in combination with "polyol (a), polyisocyanate (b) And the (meth) acrylic compound (B) represented by the following general formula (1) and / or the general formula (2) are reacted with the urethane prepolymer (A) (A) and the (meth) acrylic compound (B) in a ratio of 100: 1 to 30 (mass ratio), and then the urethane prepolymer composition is added to the urethane prepolymer composition Based polyurethane resin composition obtained by dispersing in water such that the concentration of the urethane prepolymer (A) in the obtained aqueous dispersion is 10 to 70% by mass, and reacting the urethane prepolymer (A) in the obtained aqueous dispersion with the chain extender (C) Do There is no other choice.

(additive)

Additives may be added to the waterborne polyurethane resin composition of the present invention within a range not to impair the effect of the present invention. As the additive, various general resin additives can be used without limitation. Examples of such additives include crosslinking agents, various endurance agents (hindered amine-based light stabilizers, ultraviolet absorbers and antioxidants), silane coupling agents which make the adhesion to the substrate particularly strong, colloidal silica or colloidal alumina A colorant, an inorganic colloidal sol, a tetraalkoxysilane and a condensate thereof, a chelating agent, an epoxy compound, a pigment, a dye, a film forming aid, a curing agent, an external crosslinking agent, a viscosity adjusting agent, a leveling agent, a defoaming agent, Antistatic agents such as antistatic agents, heat resistance imparting agents, inorganic or organic fillers, plasticizers, lubricants, antistatic agents such as fluorine or siloxane systems, reinforcing agents, catalysts, thixotropic agents, waxes, antifoggants, antimicrobial agents, antifungal agents, Rustproofing agents and the like can be used.

Examples of the crosslinking agent include an amino resin, a multifunctional epoxy compound comprising an adduct of urea, melamine, benzoguanamine and the like and an adduct of formaldehyde, an alkyl ether compound containing the adduct and an alcohol unit having 1 to 6 carbon atoms, and the like; Polyfunctional isocyanate compounds; Block isocyanate compounds; Polyfunctional aziridine compounds, and the like. Specific examples thereof include an oxazoline compound, an epoxy compound, a carbodiimide compound, an aziridine compound, a melamine compound and a zinc complex.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis 2-hydroxybenzophenone); 2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone; Benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy- (3-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di (3-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzoate 2- (2-hydroxy-3- (2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, (Methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- , 2- [2-hydroxy-5- (2-methoxyphenyl) -5-tert-butylphenyl] Methacryloyloxy ) Phenyl] benzotriazole, 2- [2-hydroxy-3- tert -butyl-5- (2-methacryloyloxyethyl) 3-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy- 2- (2-hydroxy-4- (3-methacryloyloxymethyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxyphenyl) benzothiazole such as 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole, Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4- dimethylphenyl) 2- [2-hydroxy-4- (3-C12 to C13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4- dimethylphenyl) (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- Dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2- 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as methyl-4-hexyloxyphenyl) -1,3,5-triazine; 4-hydroxybenzoate, octyl (3,5-dodecyl 3-butyl-4,5-dodecylbenzyl) (3,5-dodecyl 3-butyl-4-hydroxy) benzoate, tetradecyl (3,5-dodecylbutyl-4-hydroxy) benzoate, hexadecyl (3,5-dodecyl 3-butyl-4-hydroxy) benzoate, behenyl (3,5-dodecyl 3-butyl- -Hydroxy) benzoate; Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; Cyanoacrylates such as ethyl- alpha -cyano-beta, beta -diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; And various metal salts or metal chelates such as salts or chelates of nickel or chromium.

Examples of the antioxidant include phosphorus antioxidants, phenol antioxidants, and sulfur antioxidants. Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-dodecylbutylphenyl) phosphite, tris (2,5-dodecylbutylphenyl) phosphite, tris (nonylphenyl) phosphite , Tris (dynonylphenyl) phosphite, tris (mono, di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-dodecylbutylphenyl) octylphosphite, Dicyclohexylphosphite, tributylphosphite, diphenyldecylphosphite, diphenyloctylphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyldiisodecylphosphite, tributylphosphite, tris (2-ethylhexyl) , Triarylphosphite, dibutyl acid phosphite, tauryl acid phosphite, trirauryl triisopropoxide, bis (neopentylglycol) -1,4-cyclohexane dimethyldiphosphite, Bis (2,4- (2,5-dodecylbutylphenyl) pentaerythritol diphosphite, bis (2,6-dodecylbutyl-4-methylphenyl) pentaerythritol diphosphite, bis Bis (2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (mixed alkyl of C12 alkyl-C15 alkyl) -4,4'-isopropylidene Diphenylphosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)] -isopropylidene diphenylphosphite, tetra-tridecyl-4,4'-butyrylidene bis 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetra Tris (2 - [(2,4,7,9-tetrakis-tert-butyldibenzo [d, f] [1,3 , 2] dioxaphosphper-6-yl) oxy] Oxo-10-phosphaphenanthrene-10-oxide, tris (2 - [(2,4,8,10-tetrakis- tert- butyldibenzo [d, yl] oxy] ethylamine, 2- (1,1-dimethylethyl) -6-methyl-4- [3- [[2,4, Dibenzo [d, f] [1,3,2] dioxaphosphper-6-yl] oxy] propyl] phenol, and 2-butyl- -Ethylpropane diol-2,4,6-triazine tert-butylphenol monophosphite and the like can be used.

Examples of the phenolic antioxidant include 2,6-dodecylbutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5- Hydroxyphenyl) propionate, distearyl (3,5-dodecyl 3-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-dodecyl 3-hydroxy- (3-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (3,5-dodecyl 3-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl- ), Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butyrylidene bis ), 4,4'-butylidenebis (6- tert -butyl-3-methylphenol), 2,2'-ethylidenebis (4,6-dodecylbutylphenol) Tris (2-methyl-4-hydroxy-5-tert-butylphenyl (3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2, 3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-dodecyl 3-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-dodecylbutyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [ Hydroxyphenyl) propionyloxy] isocyanurate, tetrakis [methylene-3- (3 ', 5'-dodecylbutyl-4'-hydroxyphenyl) propionate] methane , 3-tert-butyl-4-methyl-6- (2-acryloyloxy-3- tert- -Hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [ 3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] It may be used, such as tocopherols.

Examples of the sulfur antioxidant include dialkyl thioiodipropionates such as thaauryl, thymyrstyl, myristyl stearyl and distearyl ester of thiodopropionic acid, and pentaerythritol tetra (? -Dodecyl Amyl mercaptopropionate esters of polyols such as poly (methyl methacrylate), poly

The amount of the endurance agent (hindered amine light stabilizer, ultraviolet absorber and antioxidant) to be used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 10 parts by mass based on 100 parts by mass of the solid content of the aqueous polyurethane resin composition. 5 parts by mass. If the amount of the lubricant is less than 0.001 part by mass based on 100 parts by mass of the solid content, a sufficient addition effect may not be obtained. If the amount of the lubricant is more than 10 parts by mass based on 100 parts by mass of the solid content, the water dispersion stability and physical properties of the coating film may be adversely affected.

Examples of the method for adding these endurance agents include a method of adding the urethane prepolymer to the polyol, a method of adding the urethane prepolymer to the urethane prepolymer, a method of adding the urethane prepolymer to the aqueous phase during water dispersion, Or a method of adding water after dispersion. From the viewpoint of easy operation, it is preferable to add the raw polyol and the urethane prepolymer.

[Optical film]

The optical film is a laminate in which an optically anisotropic layer containing a liquid crystalline compound is laminated on one side of a transparent support and a hard coat layer is laminated on the opposite side. Such an optical film is, for example, a polarizer protective film, a retardation film, a viewing angle compensation film, a light diffusion film, a reflection film, an antireflection film, an antiglare film, a conductive film for a touch panel, The aqueous polyurethane resin composition of the present invention can be used for such an optical film. The optical film to which the aqueous polyurethane resin composition of the present invention is applied is preferably a light diffusion film, a reflective film, or a prism sheet, more preferably a prism sheet.

[Prism sheet]

The prism sheet is produced by attaching a photo-curable resin such as acrylic resin, urethane acrylate, or epoxy acrylate to a sheet-like plastic substrate and a photo-curing agent. The waterborne polyurethane resin composition of the present invention is suitable as a binder for interposing a plastic substrate and a cured product of a photocurable resin, that is, this adhesive layer (easy adhesion layer). Such a prism sheet can be produced in the following order. First, an aqueous polyurethane resin composition of the present invention is applied to a plastic substrate, and then a photo-curable resin is laminated. The photo-curable resin is cured by irradiating light such as ultraviolet rays to the photo-curable resin. Thus, the cured product is not peeled off from the plastic substrate, and a prism sheet can be obtained.

As the plastic substrate, there can be used without limitation any material capable of providing a photocurable resin in a prism row shape thereon. Examples of the resin include silicone resin, acrylic resin, epoxy resin, fluororesin, polystyrene resin, vinyl chloride resin, PC (polycarbonate), PBT (Polyethylene naphthalate), PET (polyethylene terephthalate), COP (cycloolefin polymer), TAC (triacetyl cellulose) and the like can be used. PET, which is readily available at low cost, is preferable as a plastic substrate.

The method of applying the aqueous polyurethane resin composition of the present invention to a plastic substrate is not particularly limited. As such a coating method, for example, a slit coater method such as a curtain flow coater method or a die coater method, a knife coater method, a roll coater method, or the like can be used.

Examples of the photocuring agent include 2-2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-cyclohexyl-phenyl-ketone, benzyl diphenylsulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl- (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenyl-isoquinoline- Photoinitiators such as phosphine oxide can be used.

Example

Hereinafter, the present invention will be described in detail with reference to examples. In the following Examples and the like, the compounding ratio (%) means a ratio on a mass basis unless otherwise specified.

[Example 1]

(Preparation and evaluation of waterborne polyurethane resin composition U-1)

UH-CARBO200 (a polycarbonate diol having a number average molecular weight of 2000, corresponding to the polyol (a-HM) as the polyol (a) was placed in a 5-opening separable round bottom flask equipped with a Dimroth, , UB-CARBO50 (a polycarbonate diol having a number average molecular weight of 500, manufactured by Ube Gosan Co., Ltd.) corresponding to the polyol (a-LM) (b), 41.2 g of dimethylolpropionic acid as an anionic group-introducing agent (c), 163.5 g of methyl ethyl ketone (MEK) as a solvent, Respectively. Based on this formulation, the acid value of the urethane prepolymer to be produced was determined to be 45.2 mgKOH / g. The raw material mixture was reacted at 80 캜 for 6 hours to prepare a urethane prepolymer containing MEK. The acid value of the urethane prepolymer containing MEK was measured to be 27.9 mgKOH / g.

The obtained urethane prepolymer was cooled to 60 占 폚 and 31.1 g of triethylamine and 42.3 g of BPE-200 (ethoxylated bisphenol A dimethacrylate, Shin Nakamura Kagaku Kogyo Co., Ltd., Ltd.) was added, and the mixture was stirred for 30 minutes to prepare a urethane prepolymer composition. At this time, the content of BPE-200 corresponds to 11.1 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

660 g of water at 40 占 폚, 2.1 g of triethylamine and 0.1 g of adductate B-1016 (antifoaming agent, manufactured by ADEKA) were added to a 2 L disposable cup and stirred with a disper for 5 minutes, 506.8 g of the yreteen prepolymer composition was added for 2 minutes and stirred for 30 minutes. Thereafter, 32.4 g of an aqueous solution of ethylenediamine / water = 1/3 (by mass ratio) was added, and stirring was further carried out for 30 minutes. Thereafter, the temperature was raised to 40 DEG C, and MEK was removed under reduced pressure. Thus, the aqueous polyurethane resin composition U-1 of the present invention was obtained.

The U-1 was coated on one side of the corona-treated PET film using a bar coater so that the film thickness after drying was 1 占 퐉, dried at 25 占 폚 for 30 minutes and at 180 占 폚 for 10 minutes to obtain PET A test piece coated with a film of urethane resin on one side of the film was obtained. Table 1 shows the results of evaluating the moisture resistance transparency test, the adhesion test with the UV cured resin, the warp test, and the blocking test using the test pieces.

≪ Humidity transparency test >

The test piece was allowed to stand in a constant temperature and humidity bath at 80 DEG C and 80% RH for 500 hours. Thereafter, the haze value of the test piece was measured with a haze meter (NDH-5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). The haze value of the PET film alone was also measured and a value (? H) obtained by subtracting the haze value of the PET film from the haze value of the test piece was calculated. Using the calculated values, the moisture resistance of the test piece was evaluated as follows.

A: ΔH is less than 0.5.

B:? H is not less than 0.5 and less than 1.0.

C:? H is 1.0 or more and less than 2.0.

D: ΔH is 2.0 or more.

<Adhesion Test>

ADEKA OPTOMER-HC-211-9 (acrylic resin, manufactured by ADEKA CORPORATION) was applied on the surface of the test piece coated with the urethane resin film using a bar coater so that the film thickness after curing became 3 탆 Respectively. The coated film was dried at 80 占 폚 for 1 minute and UV irradiation was conducted by a metal halide lamp (intensity: 600 mW / cm ² , cumulative light amount: 500 mJ / cm ² ) to cure the acrylic resin in the coating film.

The surface of the urethane resin film on which the cured acrylic resin was adhered was cut into 100 sheets by a cutter guide having a gap of 1 mm in accordance with JIS-K5600-5-6. The adhesion of the acrylic resin cured product to the cut samples was observed, and the adhesion between the base film and the acrylic resin cured product of each sample was evaluated as follows.

A: All of the 100 pieces cut off are attached to the urethane resin.

B: Of the 100 masses cut out, 90 to 99 masses are attached to the urethane resin.

C: Of the 100 masses cut out, 80 to 89 masses are attached to the urethane resin.

D: Out of the 100 cuts, only 79 or less masses are attached to the urethane resin.

<Flexure Test>

The urethane resin film with the cured acrylic resin prepared in the adhesion test was allowed to stand at 25 占 폚 for 24 hours and the change in shape of the film was visually observed to evaluate the degree of warpage as follows.

A: Since the shape of the film is not changed at all, it can be used (pass *).

B: The film is slightly warped but can be used (pass *).

C: The film is greatly bent and can not be used.

(* A prism sheet obtained by adding a urethane resin film having a cured acrylic resin to a film such as PET is difficult to apply to a liquid crystal display or the like when the film is largely bent. In this evaluation, evaluation A or B was passed .)

<Blocking test>

Two sheets of the urethane resin film used in the moisture-proof transparency test were laminated together with the surfaces coated with the urethane resin film, and sandwiched using a glass plate and a buffer. A load of 10 kgf was applied thereto, and the sample was allowed to stand under an atmosphere of 60 DEG C and 80% RH for 24 hours. Thereafter, the overlapped test piece was peeled off and the breakage state was visually observed. From the observation results, the blocking resistance of the urethane resin film was evaluated as follows.

A: The same state as before the blocking test, and the film was not damaged at all.

B: A part (0.1 to less than 10%) of the entire area of the film is broken.

C: Less than 10% and less than 50% of the entire area of the film is broken.

D: More than 50% of the entire area of the film is broken.

[Examples 2 to 4]

(Preparation and evaluation of waterborne polyurethane resin compositions U-2, U-3 and U-4)

2, U-3 and U-4 were prepared in the same manner as in Example 1, except that the (meth) acrylic compound (B) The films using the water-based polyurethane resin compositions U-2, U-3 and U-4 were evaluated from the same viewpoint as in Example 1. [ The evaluation results are shown in Table 1.

[Example 5]

(Preparation and evaluation of aqueous polyurethane resin composition U-5)

54.6 g of UH-CARBO200 (homologous) and 54.6 g of UH-CARBO50 (homologous) as a polyol (a) were added to a 5-opening separable round bottom flask equipped with a thermometer, a stirrer, dicyclohexylmethane diisocyanate as an anionic group-introducing agent (b), 54.6 g of dimethylolpropionic acid as an anionic group-introducing agent (c) and 155.1 g of methyl ethyl ketone (MEK) did. Based on this formulation, the acid value of the urethane prepolymer to be produced was determined to be 60.5 mgKOH / g. The raw material mixture was reacted at 80 캜 for 6 hours to prepare a urethane prepolymer containing MEK. The acid value of the urethane prepolymer containing MEK was determined to be 36.8 mgKOH / g.

The obtained urethane prepolymer was cooled to 60 占 폚 and 41.0 g of triethylamine and 46.2 g of BPE-200 as the (meth) acrylic compound (B) were added and stirred for 30 minutes to obtain a urethane prepolymer composition . At this time, the content of BPE-200 corresponds to 12.2 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A).

1170 g of water at 40 캜, 2.9 g of triethylamine and 0.1 g of adductate B-1016 were added to a 2 L disposable cup and stirred with a disper for 5 minutes. Then, 506.8 g of the urethane prepolymer composition , And the mixture was stirred for 30 minutes. Thereafter, 32.4 g of an aqueous solution of ethylenediamine / water = 1/3 (by mass ratio) was added, and stirring was further carried out for 30 minutes. Thereafter, the mixture was heated to 40 占 폚 and MEK was removed under reduced pressure to obtain an aqueous polyurethane resin composition U-5. A film using the aqueous polyurethane resin composition U-5 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 6]

(Preparation and evaluation of aqueous polyurethane resin composition U-6)

An aqueous polyurethane resin composition U-6 was prepared in the same manner as in Example 1 except that 110.6 g of BPE-200 was used. A film using an aqueous polyurethane resin U-6 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 7]

(Preparation and evaluation of aqueous polyurethane resin composition U-7)

An aqueous polyurethane resin composition U-7 was produced in the same manner as in Example 1 except that 21.0 g of BPE-200 was used, and the humidity resistance transparency test, the adhesion test with UV cured resin, the warpage test and the blocking test were evaluated . The evaluation results are shown in Table 1.

[Comparative Example 1]

(Meth) acrylic compound (B).

(Preparation and evaluation of comparative water-based polyurethane resin composition U-8)

Except that A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Kagaku Kogyo K.K.) was used in place of BPE-200 as the (meth) acrylic compound (B) To prepare a resin composition. Thus, a comparative waterborne polyurethane resin composition U-8 was obtained. A film using an aqueous polyurethane resin U-8 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 2]

(Meth) acrylic compound (B).

(Preparation and evaluation of comparative water-based polyurethane resin composition U-9)

Aqueous polyurethane resin composition was prepared in the same manner as in Comparative Example 1 except that 110.6 g of A-TMMT was used as the (meth) acrylic compound (B). Thus, a comparative water-based polyurethane resin composition U-9 was obtained. A film using an aqueous polyurethane resin U-9 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 3]

(Meth) acrylic compound (B).

(Preparation and evaluation of comparative water-based polyurethane resin composition U-10)

Except that AM-90G (methoxypolyethylene glycol # 400 acrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.) was used instead of BPE-200 as the (meth) acrylic compound (B) To prepare a polyurethane resin composition. Thus, a comparative waterborne polyurethane resin composition U-10 was obtained. A film using an aqueous polyurethane resin U-10 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 4]

(Meth) acrylic compound (B) is not used.

(Preparation and evaluation of comparative aqueous polyurethane resin composition U-11)

An aqueous polyurethane resin composition was prepared in the same manner as in Example 1 except that the (meth) acrylic compound (B) was not added to the urethane prepolymer. Thus, a comparative waterborne polyurethane resin composition U-11 was obtained. A film using the aqueous polyurethane resin composition U-11 was evaluated in the same manner as in Example 1. [ The evaluation results are shown in Table 1.

[Comparative Example 5]

(Meth) acrylic compound (B) in an excess amount.

(Preparation and evaluation of comparative water-based polyurethane resin composition U-12)

A urethane prepolymer was prepared under the same conditions as in Example 1. The obtained urethane prepolymer was cooled to 60 캜 and 31.1 g of triethylamine and 190.7 g of BPE-200 as the (meth) acrylic compound (B) were added and stirred for 30 minutes to prepare a urethane prepolymer composition did. At this time, the content of BPE-200 corresponds to 50.0 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

660 g of water at 40 캜, 2.1 g of triethylamine and 0.1 g of adductate B-1016 were added to a 2 L disposable cup and stirred with a disper for 5 minutes. Then, 506.8 g of the above yreteen prepolymer composition , And the mixture was stirred for 30 minutes. Thereafter, 32.4 g of an aqueous solution of ethylenediamine / water = 1/3 (by mass ratio) was added, and stirring was further carried out for 30 minutes. Thus, a comparative water-based polyurethane resin composition U-12 was obtained. When the aqueous polyurethane resin composition U-12 was visually confirmed, it was found that some components were separated. IR analysis showed that the isolated component was BPE-200. As to the waterborne polyurethane resin composition U-12, no evaluation was made for moisture resistance transparency test, adhesion test with UV cured resin, warping test, and blocking test.

[Table 1]

(Annotation in Table 1)

** 1: ABE-300: ethoxylated bisphenol A diacrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.

**: EA-0200: a diacrylate of formula (1) wherein R ¹ and R ² are hydrogen atoms, R ³ and R ⁴ are ethylene groups, and R ⁵ is the formula (3-7) Compound, manufactured by Osaka Gas Chemical Co., Ltd.

** 3: A-9300S: ethoxylated isocyanuric acid triacrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.

As shown by the evaluation results in Table 1, the comparative water-based polyurethane composition U-11 in which the (meth) acrylic compound (B) was not blended was inferior in adhesion to the photocurable resin, . 8, U-9, and U-10, which did not use any of the predetermined compounds of the present invention as the (meth) acrylic compound (B), exhibited excellent water fastness to moisture, transparency, , It is not suitable for optical film applications. The comparative water-based polyurethane composition U-12 in which the (meth) acrylic compound (B) was excessively blended had its components separated, which made film processing itself difficult. On the contrary, the evaluations of U-1, U-2, U-3 and U-4 corresponding to the water-based polyurethane composition of the present invention were evaluated to be acceptable in terms of moisture resistance transparency, adhesion, warpage and blocking resistance .

It was confirmed that the urethane film using the aqueous polyurethane resin composition of the present invention was excellent in moisture resistance and transparency, and had good adhesion to a cured product of an acrylic resin. It was also confirmed that the film obtained by laminating the cured product of the PET film and the acrylic resin through the layer of the aqueous polyurethane resin composition of the present invention had little warpage with time. It was confirmed that when the films made of the waterborne polyurethane resin composition of the present invention were overlapped with each other, the blocking was also small. As described above, the water-based urethane resin composition of the present invention is excellent in light transmittance, heat resistance, adhesion to polyester base film and photo-curable resin, and blocking resistance.

Industrial availability

The waterborne polyurethane resin composition of the present invention having good adhesiveness to an acrylic resin cured product is useful as a contact wear film which functions as a binder of a photocurable resin and a PET film used in a prism sheet. It is considered that the optical film using the water-based polyurethane resin composition of the present invention as the binder of the present invention shows good performance while maintaining the brightness, in that the water-based polyurethane resin composition of the present invention is also excellent in moisture and moisture transparency. In addition, blocking between the films made of the waterborne polyurethane resin composition of the present invention is suppressed, and overlapping is possible. Therefore, the workability of the film made of the aqueous polyurethane resin composition of the present invention is good. The waterborne polyurethane resin composition of the present invention can be applied to various optical films used in displays such as liquid crystal televisions and personal computers. The present invention is very useful in industry.

Claims (8)

A urethane prepolymer (A) obtained by reacting a polyol (a), a polyisocyanate (b) and an anionic group-introducing agent (c) A urethane prepolymer composition comprising the (meth) acrylic compound (B) so that the proportion of the yretin prepolymer (A) and the (meth) acrylic compound (B) is 100: 1 to 30 (mass ratio) And then the urethane prepolymer composition is dispersed in water such that the concentration of the urethane prepolymer composition is 10 to 70% by mass, and the urethane prepolymer (A) in the obtained aqueous dispersion is dispersed in the extender (C) Based on the weight of the aqueous polyurethane resin composition.

(Wherein R ¹ and R ² each independently represents a hydrogen atom or a methyl group, R ³ and R ⁴ each independently represent a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ⁵ represents a sulfur atom or a divalent hydrocarbon group and m and n each represent an integer of 0 to 10.)

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represent a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group) The method according to claim 1,
Wherein the (meth) acrylic compound (B) is a compound represented by the general formula (1), and R ⁵ in the general formula (1) is a single bond, a methylene group, -CH (CH ₃ ) (CH ₃ ) ₂ -, and any one of the functional groups represented by the following general formulas (3-1) to (3-7).

(m represents an integer of 4 to 12) The method according to claim 1 or 2,
Wherein the polyol (a) is at least one or more selected from the group consisting of a polyester polyol (a1), a polycarbonate diol (a2), a polyether polyol (a3) A urethane resin composition. The method according to any one of claims 1 to 3,
Wherein the polyol (a) is at least one or more selected from a polycarbonate diol (a2). The method according to any one of claims 1 to 4,
Characterized in that the polyol (a) comprises a high molecular weight polyol (a-HM) having a number average molecular weight of 1,500 to 5,000 and a low molecular weight polyol (a-LM) having a number average molecular weight of 300 to 1,000, Retin resin composition. The method according to any one of claims 1 to 5,
Wherein the yesterin prepolymer (A) has an acid value in the range of 30 to 80 mgKOH / g. An optical film comprising the aqueous polyurethane resin composition according to any one of claims 1 to 6. A prism sheet comprising a layer comprising an aqueous polyurethane resin composition according to any one of claims 1 to 6, a base film, and a layer of a cured product of a photocurable resin.